Process for sulphating olefines



Patented Jan. 21, 1936 UNITED STATES PROCESS FOR SULPHATING OLEFINESRobert F. Le Baron, New York, N. Y., assignor,

by mesne assignmen Company, Wilmington Delaware ts, to Standard AlcoholDel.,'a corporation of Application April 4, 1930, Serial No. 441,623

7 Claims. (01. 26099.12)

The phrase petroleum oil as herein employed, denotes generically crudepetroleum, and/or the normally liquid distillates derived therefrom.When such petroleum oil is cracked to produce gasoline, a practicallyunbroken series of hydrocarbons is obtained ranging from hydrocarbonscorresponding to the oil cracked through kerosene, gasolineand normallygaseous hydrocarbons up to and including methane. Where the cracking isrelatively mild as, for example, cracking carried out in liquid phaseunder pressures up to about 1000 pounds per square inch, the productscontain olefinestogether with substantial proportions of parafilnes.Where cracking is more extensive as, for example, cracking carried outin liquid phase under pressures in excess of 400 pounds per square inch,or in vapor phase at any pressure, the proportipn of parafiines isrelatively less; but there is a proportionate increase in the amount ofdi, tertiary and higher olefines present. In eithercase, the sulphationof the olefines presents difficulties not found in treating the pureolefines owing to the diluting influence of the paraii'ine hydrocarbons,and/or to a variety of chemical difliculties introduced by the presenceof the di, tertiary and higheroleflnes.

It has heretofore been proposed 'to sulphate the butylenes and amylenesby separating from the products of cracking, a fraction the oleflnecontent of which consists predominantly of olefines of a single numberof carbon atoms corresponding to the particular olefine to be sulphated,and this procedure has to an extent minimized the difflculties, inasmuchas it permits the use of a concentration of sulphuric acid which isoptimum for the particular olefine to be sulphated, and eliminates fromthe reaction zone olefines of higher molecular weight which wouldcomplicate the process both by polymerizing with each other and with theparticular olefine to be sulphated. These fractions containingpredominantly gaseous olefines of a single number of carbon atoms to themolecule, viz, the olefines of from 2 to 4 carbon atoms both inclusive,have been treated in gas phase. I am aware that butenes have to someextent been treated in, liquid phase in solution in amylenes, but thehydrocarbon fraction derived from the products of cracking petroleum oilthe olefine content of which consists predominantly of olefines of 4carbon atoms to the molecule, has heretofore been treated only in gasphase. I have found that this treatment in gas phase is invariablyaccompanied by the loss through polymerization of very substantialproportions of the particular oleflne to be sulphated, and that thisloss may be very substantially avoided by reacting on said suchfractions in liquid phase.

The reaction in liquid phase may be carried out more selectively andeflectually and renders possible the successful employment of acidstrengths which would be comparatively ineffective if applied to the gasphase material with a very substantial diminution in the extent to whichthe material is polymerized. As a specific example, the fractioncontaining olefines of 4 carbon atoms to the molecule has heretoforebeen treated in gas phase with aqueous sulphuric acid of 77% or higherconcentration for the sulphation of the secondary olefines containedtherein. I have found that the employment of this strength of acidinvolves the polymerization of substantial quantities and, inmany cases,the

aqueous sulphuric acid 01' from to to H2804 content. In particular, Ifind a strength of from 68 to 70 to 72% to give a highly satisfactoryreaction rate with relatively little polymerization and exceptional easeof control. Such a butene traction normally contains tertiary buteneswhich should, for best results, be selectively removed prior to thesulphation of the secondary butenes contained therein. The efliciency ofthe final sulphation of the secondary butenes is conditioned largely onthe extent to which the tertiary butenes have been removed. In thisconnection, I have found that the tertiary butenes may be more cleanlyand selectively separated by admixing such a fraction in liquid phasewith aqueous sulphuric acid. I may employ for this purpose sulphuricacid of from 0 60 to 65%, H2804 content, at temperatures below 20 C.;but owing to the improved emciency which I have found to be associatedwith the I liquid phase reaction on such a fraction, I now find that Ican cut the tertiary olefines cleanly 45 and selectively without in anymeasurable degree polymerizing the dioleflnes by treating such afraction in liquid phase with aqueous sulphuric acid of from 55 to 60%,H2SO4 content. Not only does this effect an improvement, per se, in the50 eiiiciency of removal of the tertiarles which is shown by thesuperior quality and higher yield of tertiary alkylsulphates from whichthe corresponding tertiary alcohols may be derived, but the subsequentsulphation of the secondary ole- 55 refrigerant is introduced by meansof pipes I I drawn through pipe I20, controlled by valveI2I,

and diverted from the system through side arm I22, controlled by valveI23, to be worked up for tertiary butyl alcohol.

erably from 68 to 7 2%, is then supplied to autoclave I30 and arelatively small stream of the remanent hydrocarbon material fromautoclave I05 is run into autoclave I 30. This is the butylene fractionafter removal of tertiary olefines therefrom. The reaction in autoclaveI is also carried out in liquid phase, and while I find it of advantageto add the olefine to the acid, this procedure may be reversed or anyalternative procedure may be followed within the purview of my inventionprovided only that the materials are retained in liquid phase.Temperatures during this operation are preferably held between 20 and 25C. by the introduction of a cooling meum through pipes I10 and III tothe jacket I12.

At the conclusion of the dilution operation the diluted acid liquor isworked up for secondary butyl alcohol.

I will now describe the processing of the propylene fraction stored intank 45. The autoclave I80 is preferably preliminarily charged with aquantity of sulphuric acid of from to H2804 content, from 68 to 72%being preferred. A quantity of the propylene fraction is then suppliedto autoclave I as a relatively small continuous stream by means of pipeI90, controlled by valve I9I and pump I92. During this stage, mixing iseffected by rotation of propeller I82 and the temperature is preferablyheld below 25 C., say between 20 and 25 0., by the introduction of acooling medium through pipes I83 and I84 to jacket I85. After completingthe addition of the propylene and mixing the materials for an additionalperiod of about one hour, the acid liquor is withdrawn through pipe 200,controlled by valve 20I, and diluted in autoclave 202 to be thereafterworked up to isopropyl alcohol. The procedure for diluting the acidliquor is similar to that applied to the butylene fraction, and need nottherefore be more fully described.

I will now describe the processing of the ethylene fraction held in.tank 85. For this purpose,

the autoclave 2I0 is preferably supplied with a batch of aqueoussulphuric acid of about 85%,

A quantity of sulphuric acid of from 65 to 75%, H2504 content, and pref-5 C. by the introduction of a refrigerant by pipes 220 and 22I to thejacket 222. Autoclave 2I0 is equipped to carry the vapor pressures ofethylene in liquid phase and the reaction is carried out on the materialin this condition. After 5 conclusion of the addition of the ethylenefraction which may require several hours, the material in autoclave 2| 0are subjected to further mixing for a period of 3 or 4 hours and thendischarged through pipe 230, controlled by valve 23I and distributor232, into autoclave 233. Autoclave 233 is preliminarily charged withwater for dilution of the acid liquor, and, inasmuch as this operationdoes not differ materially from the dilution of the butylene acidliquor, it will not 15 be more fully described.

The foregoing specific description merely illustrates one specificprocedure by which my invention will be carried into effect and isfurnished for purposes of illustration and not by way of limita- 20tion. It is my intention that the invention be limited only by theappended claims or their equivalents in which I have endeavored to claimbroadly all inherent novelty.

I claim:

1. Process of sulphating secondary butene contained in a mixture ofhydrocarbons produced by cracking petroleum oil, which comprisesseparating from said mixture by distillation a fraction, the olefinecontent of which consists pre- 30 dominantly of a mixture of branchedand straight chain olefines having four carbon atoms to the molecule,and admixing said fraction in liquid phase with aqueous sulphuric acidof from 50-60% H2804 content, removing the aqueous acid layer 85 andadmixing the residual hydrocarbons in liquid phase with aqueoussulphuric acidof from 65 to 70%, H2804 content.

2. Process of sulphating secondary butene contained in a mixture ofhydrocarbons produced by cracking petroleum oil, which comprisesseparating from said mixture by distillation a fraction, the olefinecontent of which consists predominantly of secondary and tertiaryolefines of four carbon atoms to the molecule, selectively removingtertiary olefines from said fraction by contacting with aqueoussulphuric acid of from 50-60% H2804 content, removing the aqueous acidlayer with the tertiary olefines in solution, and thereafter sulphatingthe secondary olefines contained in said fraction by admixing saidfraction in liquid phase with aqueous sulphuric acid of from 65 to 70%,H2S04 content.

3. Process of sulphating secondary butene contained in a mixture ofhydrocarbons produced by cracking petroleum oil and containing bothsecondary and tertiary olefines of four carbon atoms to the molecule,which comprises separating from said mixture by distillation a fraction,the olefine content of which consists predominantly of secondary andtertiary olefines of four carbon atoms to the molecule, selectivelyremoving tertiary olefines from said fraction by admixing said fractionin liquid phase with 55 to 60% sulphuric acid, and thereafter sulphatingthe secondary olefines contained in said fraction by admixing saidfraction in liquid phase with aqueous sulphuric acid.

4. Process according to claim 3, in which the selective removal oftertiary olefines is accomplished by admixing said fraction in liquidphase with sulphuric acid of from 55 to 60%, H2804 content, attemperatures not exceeding 20 C.

5. Process of sulphating secondary butene contained in a mixture ofhydrocarbons produced by 75 cracking petroleum oil and containing bothsecondary and tertiary oleflnes, which comprises separating from saidmixture by distillation a fraction, the olefine content of whichconsists predominantly of secondary and tertiary oleflnes of four carbonatoms to the molecule, selectively removing tertiary oleflnes from saidfraction by admixing said traction in liquid'phase with aqueoussulphuric acid, and thereafter sulphating the secondary oleflnescontained in said fraction by admixing said fraction in liquid phasewith aqueous sulphuric acid of from 65 to 70%,

H2804 content.

6. Process according to claim 5, in which the selective removal oftertiary oleflnes is accomplished by admixing said fraction in liquidphase with aqueous sulphuric acid 01 from 55 to 60%, H2804 content.

'7. Process according to claim 5, in which the selective removal oftertiary oleflnes is. accomplished by admixing said fraction in liquidphase with aqueous sulphuric acid 01 from 55 to 60%,

H2804 content, at temperatures not exceeding 1 ROBERT F. LE BARON.

Jan. 21, 1936. EW 2,028,227

' MOTOR 'TRUQK Filed June 25; 1935 2 Sheets-Sheet l IgVEN TOR.

BY Z5 AZRNEY.

